Contact tower reactor for vapor phase nitration



Nov. 20, 1951 STENGEL ETAL 2,575,855

CONTACT TOWER REACTOR FOR VAPOR PHASE NITRATION v Original Filed July 22, 1944 l 2 SHEETS-SHEET l FIG.I.

INVENTORS 1 L. A. STENGEL ET AL 2,575,855

CONTACT TOWER REACTOR FOR VAPOR PHASE NITRATION FIG. 1

INVENTORS M m awswwg.

B 1 m CW.

Patented Nov. 20, 1951 CONTACT TOWER REACTOR FOR VAPOR PHASE NITRATION Leonard A. Stengel and Richard S. Egly, Terre Haute, Ind., assignors to Commercial Solvents Corporation, Terre Haute, Ind., a corporation of Maryland Original application July 22, 1944, Serial No. 546,186. Divided and this application June 17, 1946, Serial No. 677,236

1 Claim. 1

This invention relates to the vapor phase nitration of alkanes, and more particularly to a method and apparatus for improving the efiiciency of the process.

In carrying out vapor phase nitration of al kanes in the past, it has been the practice to separately vaporize the reactants, that is, the alkane and nitric acid, and to mix the vapors in a mixing chamber, thereafter to pass the combined vapors to a reaction chamber, and there to supply heat sutficient to bring the mixture to the reaction temperature, thereby causing the components to react to produce the desired nitroalkanes.

This prior practice was subject to a number of disadvantages. Not only is the nitration reaction an exothermic one, but it is a reaction which proceeds favorably only within a relatively narrow temperature range to give optimum yields of nitroalkanes. Thus, although nitration will occur to some extent within a relatively wide temperature range between approximately 360 C. and 480 C., it is only within the relatively much narrower range of about 390 C. and 440 C. thatoptimum nitroalkane yields are obtained. Thus, it is necessary, after the initiation of the nitration reaction, to remove the heat of reaction rapidly enou h and to such an extent that the favorable reaction temperature range is not exceeded and yet not to remove so much heat that the mixture is cooled below its favorable reaction temperatures. This thermal control was formerly accomplished by immersing the reaction chamber in a heat absorbing jacket or bath such as a salt bath to absorb and convey away the excess heat of reaction. Such an operation was not only wasteful of heat and heat transfer, but due to the extreme rapidity of the reaction it was often impossible to remove the generated heat rapidly enough to prevent high temperatures from being reached, with resulting lowering of nitroalkane yields.

Another disadvantage of the prior art practice was the low mole ratios of alkane to nitric acid that necessarily resulted from the prior practice of mixing the vapors before passing them to the reaction chamber. The higher the mole ratio of alkane to nitric acid, up to perhaps 40 to 1, the higher the yield of nitroalkane. But high mole ratios were uneconomic to maintain in the prior art system, because of the excessive amounts of unreacted alkanes which had to be recovered from the exit gases. In the prior art practice, about the highest mole ratioswhich could be used, and still maintain an economic process with respect to recovery of unreacted alkanes and the like, was around 6 to 1.

We have now found that the disadvantages of the prior art can be overcome by our process in which the reactants are mixed, and the nitric acid reactant is vaporized, and the reaction takes place, all in a single combined vaporization-reaction chamber, and in which the temperature of the reaction is readily maintained within the relatively narrow range favorable for the production of high yields of nitroalkanes and high effective mole ratios of alkane to nitric acid conducive to high yields are utilized while still maintaining an economic process with respect to the recovery of unreacted alkanes and the like.

In practicing our invention, we preheat only the alkane reactant with which is then mixed successive limited portions of liquid nitric acid of predetermined concentration, such that the heat of the ensuing reaction is utilized to vaporize the nitric acid, and is thus dissipated and largely controlled within the reaction system to maintain the reaction temperature within the narrow optimum range described. In other words sufficient water is present in the nitric acid to raise its heat of vaporization under the conditions of the reaction to the point at which this heat substantially balances the heat of reaction of the acid with the alkane. The successive small additions of acid not only contribute, as described hereinafter, to the control of reaction temperature but bring about a condition in which the actual mole ratio of alkane to nitric acid at any stage of the process is high, while the overall ratio of total alkane to total nitric acid passing through the system is within the range of mole ratios of the prior art practice found to be economic with respect to alkane recovery. Our invention relates particularly to the nitration of the lower alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, and the like.

In the drawings, Figure I is a schematic representation of the apparatus of our invention. Figure II is a detail showing the alkane inlet and a suitable nozzle for atomizing the liquid nitric acid into the stream of preheated alkane vapor. Figure III illustrates a modification in which the alkane flows counter-current to the direction of injection of the nitric acid and in which the alkane is shown as introduced at the bottom of a vertical reactor rather than at the top as: in Figure I. Figure IV illustrates a modification of a multiple unit vaporizer-reactor in which the individual units are horizontally disposed. Like heater I2 for heating the alkanereactantcomprises a heating element l8, conventionally illustrated as a gas burner, an. inlet IQ for the. cold.

alkane, a heat exchanger 2li;,il lustrated as a coil of pipe. A gas conveyor ldzleadsflO-alkane.inlet.

21 of reaction chamber I0. Reaction chamber In is further provided with a primary inlet .14 for the first injection of liquid nitric acid disposed in the path of the incoming gaseous reactant and slightly beyond the hot gas inlet. Other supplementary liquid reactant inlets 22 are disposed at intervals through the extent of the reaction chamber.

the. reaction chamber and cooling means It; are provided and. are. shownas inlets for introducing cold inert. gases orliquids. to. the reaction. chamhen. Atemperature recorder and controllerxll is alsoiprovided, connected, to. thermocouples 25.. If. the reactants are. of corrosive. nature a. protective, corrosion resistant lining 2.3.will be provided Within reaction chamber lit. Beyond the reactionchamber or chambers, a. cooling chamber '23, is. positioned, through. which the reacted. vapors.

are-withdrawn. through outlet conduit 23; to. subsequent. recovery.

In operation, the. alkane, either gaseous or; liquid; enters preheater t2.thr0.ugh inlet l9 and passes through. heat exchanger 2.6 which is.

heatediby; heating element. It. Thehot gaseous alhane, heated to. a suitable. temperature withinv the iavorable. reaction temperaturerange. passes out of. the. preheater; and. is ledthrough. conveyor Iii to. inlet Zlof: reaction. chamber I61. The reaction chamber may be. a. single unit. with a..p1.u

Ifi-lityiQf inlets for the:- nitricv acid or may. come.

prisela. plurality of. units as shown, for greater flexibility in. controlling, the. reaction... The. liquid;

nitric acid.- is intro uced. in. omiz d form. in o the react on. hamb r at quid. inlet. i4; sli ht y beyond. the. vapor inlet. and. isvaporize nd.

. eh; h ea n ch a d con ue to a hey roc e he. quantity, o l q nitric acid added at each stage is regulated. to absorb-.the heat of reaction as it is produced and the; addition of cold liquidv is limited at any one.

stage so. asto be insufiicientto cool the reactinggasesbelow the lower limit of the favorable. temperature range of reaction. Thus thegases, in-

itially cooled somewhat at the liquid inlet, are

raised; temperature by the exothermic. reaction to the upper limit of the favorable reaction temperature. When; such a. pointis reached, ad-v ditional liquid reactant isadded as at. 22, and the vaporizatiomreaction. and absorption of heatis Heaters. i5; shown schematically as simple strip heaters are disposed at. intervals in.

erves; to; vaporize, additional ni- The reacting: vapors are iorced by a positive pressure- 4 of the gaseous reactant originally introduced is utilized.

The rate of flow of alkane is regulated relative to the rate of addition of nitric acid such that the efieotive mole ratios of alkane to nitric acid are in excess of 6 to 1 and preferably considerably higher, preferably between about 10 to 1 and 40 repeated: This. stepwise addition of liquid re-- acta'nt may be repeated until the desired portion to l. Relatively somewhat higher mole ratios should be usedin the case of methane and ethane than with the other lower alkanes because of the lower specific heats of these two alkane members.

For the lower alk-anes other than ethane and methane,- a moleratio between about 20 to 1 and unreacted alkanes, it is desirable to operate at.

as lo.w aspossible overall ratio of alkane to nitric acidand: thereforato. resort'to as many successive-additions of nitric acid as possible. However, the. number of successive additions is limited.v by thefact that as more alkane reacts to formnitroalkane, the. larger the proportion of nitroalkane which comes in contact with fresh nitric acid and when this concentrationreaches a high enough.

point, reaction and decomposition of the nitroalkane begins to take place. We have found that the number of additions should. be limited so as to maintain an. overall ratio of alkane to. nitric acid. of not more. than about 6. to. l, but preferably not less than about 3 to 1 as the presence. of about this excess of alkane is necessary to foster efficient progress, of the reaction. After reaction, thegases pass through a cooling hamrher. and are withdrawn to the recovery system. 7

The. quantity ofreaction heat absorbed may be, controlled. bycontrolling the concentration. of nitric acid employed, and by. control, of the. quantity of acid added at each step, that, is, byvarying the mole-ratios, of alkane to acid at the. time and place of injection-within the-higheffew tive..mole ratios-described. Furtherminor control.

may be effected by slightadditions of heat, par

ticularly in the vaporization zones, and slight.

' suitable means. Cooling can be effected, for.ex--

ample, by the introduction of cooling medium which may be cold gaseous alkane, or aninert.

gas: or even a inert liquid such as. water.

Themajor control, as brought out above, is;-

effected by the step-wise addition of the liquid reactant to regulate. the magnitude-oi"; reaction taking place in any desired period of time, andconsequently limiting the rate of generation of the-exothermic heat of. reaction. Externalheating and, cooling will usually be used; to, efiect minor temperature regulations, aimed at maintaining. the. temperature within. the range, most: favorable for obtainingv the particular clesired reaction products. i

This step-wise addition ofi'acid also permits. the utilization of; the high effective moleratios of-alkane to nitric acid atthe points of reaction described, while still maintaining the overall mole ratio of reactants fed through the system at ornear the low priorratios, as described;

In the nitration of propane, for example, with 75% nitric acid, under the conditions described, the heat of exothermic reaction is of the same order, but slightly less than the heat of vaporization of the acid. In this reaction, of the total nitric acid fed to the reactor, about 37% on a mole basis is converted to nitroalkanes, about 57% is reduced to nitric oxide, the remainder being lost-mostly as acid in the water formed in the reaction. A number of reaction schemes in a system including lower alkanes and nitric acid are possible among which the following are illustrative:

Regardless of which particular reactions take place, the total heat generated will be approximately the same provided the reduction product of nitric acid is nitric oxide, and this is the case in the vapor phase nitration of alkanes, so that as a practical matter it is not necessary to determine just what reactions are taking place in practice, results approximate the theoretical heat released per unit mole of nitric acid or somewhat higher and this value is approximately the same for all the lower alkanes.

In practice the acid used need not be 100% acid, as not only is this extremely diiiicult to handle, but yields of nitroalkanes appear to be more nearly optimum when the nitric acid contains certain proportions of water ranging fro-m approximately 5-55%. However, greater utilization of heat of reaction is possible if the acid to be vaporized is of a relatively high concentration. Thus, although the heat of reaction of nitric acid per se with nitroalkanes is the same regardless of the concentration, that is, if based only on the nitric acid content of the solution used, the heat required to vaporize the acid solution and raise it to reaction temperature, on the other hand, against which the heat of reaction must be balanced will depend both on the concentration of acid used, and on its initial temperature. The more concentrated the acid the greater the advantages that can be realized for this particular reaction. For example, the percent of the total required heat which can be supplied by the heat of reaction of 45% acid at 20 C., is about 43% at the mole ratios indicated. If 62% acid is used, about 64% of the necessary heat can be furnished by the heat of reaction. Using 75-78% acid the heat efficiencies are ever more favorable and substantially all of the necessary heat can be furnished by the reaction. Above this concentration, the heat of reaction begins to exceed that required to vaporize and heat the acid, so that above about 80% concentrations cooling of some kind becomes necessary. Therefore, the preferable concentrations of nitric acid to be used is in the range between about 70 and 80%.

The temperature range over which alkanes can be nitrated with nitric acid in the vapor phase to nitroalkanes varies over a range between about 360 C., and 480 0. But best yields of nitroalkanes with a minimum of undesired decomposition products and side reaction products are obtained only when the temperatures are maintained between about 390-440 C. i The reaction takes place extremelyrapidlyrequiring only a small fraction of a, second at about 430 C.

In practicing our invention, we can maintain the temperature within the favorable range and prevent it from reaching high temperatures' at which side reactions occur and decomposition sets in. In our process and apparatus, the reacting gases are propelled continuously throughthe reaction units under a positive pressure- The nitric acid added at any single point is limited in quantity in accordance with the indicated balance at any concentration betweenheat of reaction and vaporization respectively so that the evolved heat is sufiicient only to raise the temperature of the reaction mixture to the upper limit of favorable reaction conditions, namely, about 440 C. Before it exceeds this temperature, additional acid is introduced in sufilcient quantity to absorb a quantity of heat in vaporizing to lower the temperature of the mixture to the lower limit of favorable reaction, about 390 C., but not below. Slight variations can be adjusted asdescribed by heating the vaporization portions and cooling the reaction portions. The number of successive additions of acid depend on the heat balance and mole ratio factors described above, which in turn depends to some extent on the acid concentration. Using 75% nitric acid, about 5 additions of acid are .suitable to utilize the heat of reaction to advantage and to react with the. desired proportionuo'f the propane fed to the system to yield maximum conversions.

Best yields of nitroalkanes are obtained when the overall mole ratio of alkane to nitric acid is above about 4 to 1, the higher ratios producing higher yields but entailing the expense of -recovering large proportions of unreacted alkane. However, in regulating our reaction temperatures as described, the effective mole ratios at anyparticular instant are maintained at a considerably higher figure, while still maintaining the over all mole ratio low enough to keep down the volume of alkane to be recovered to an economically low figure. Thus, with an overall mole ratio of about 5 to 1, and using 5 successive additions of nitric acid of 78% concentration our initial mole ratio, that is, the mole ratio at the first nitric acid addition may be as high as 25 to 1 while the mole ratios at the successiv'e addition points will be of the order of 24 to 1, 23,to.1, 22 to 1, and. 21 to 1, respectively, depending on the quantity of alkane which has reacted in. the earlier stages.

Our invention is further illustrated by the following specific examples.

Emample I Propane was preheated to 430-435 C. and fed at the rate of 11,500 cu. ft. per hour and pound gauge pressure to the top of the first spray vaporizer-reactor section. The complete reaction chamber consisted of five spray vaporizer reactor sections. Each vaporizer-reactor unit was 6 feet long by 3 inches diameter. For 30 inches below each atomizing nozzle the stainless steel reactor wall was protected by a fused silica liner. Cold 78.0% nitric acid, at atmospheric temperature (15-25 C.) was pumped to each nozzle at the rate of 107 pounds per hour. Initial mole ratio of propane to HNOs was 24.2 to 1, overall ratio for entire nitrator was 4.84 to 1.

The temperature in the center of each vaporizer-reactor section, where the acid spray was completely vaporized but reaction was just start- 7 ins; was 4.0041? 6i Thetemperature"at'the exit end .of each vaporiaatiohl-reactioncsection was: held at approximately 425 The nitrator. was well insulated to reduce heat loss to a minimum: With 780% I-INQa, the heat'of taper ization of the acid plus losses. was sligh ly les than the heat of react on. so thattherewas a tendency for the temperature to increase a..- few degrees, as the reactants proceeded from thetop to bottomzof the. reactor. T- mainta-in steady temperatures throughout the, reactor, thatis, to hold the exit; end of .each. repudiatione ction Section approximately 425 C... a small amoun of steam 11159 .6.) was; introdu d to thos sections which tended to operate at hi her de ired tem eratures to cool. these Th main control of temperature depended n the tem perature of the preheated nrop helen t e concentraticn of. henit i an Steam wa u ed On ytfflr fin control, V Thenitroparafiins were separated from the con ensa e. a d 16. ounds e u f e age- ;molecular weight 83 were obtained. This amounted to a 30.8% conversion of the nitric a id in n trcpa tfi s.

Example II The same spray vaporizer-reactor and essentially "the same conditions were used as in the previous example except that 76% nitric acid was used. With acid of this strength the heat needed to vaporize the. acid and heat the acid vapors up to reaction temperatures. plus the heat needed to replace heat losses, .losses being kept to a minimum by four inches of insulation on the nitrator', exceeded the heat supplied :by

Therefore, with nitric acid at a concentration as low as 76% as in the present example the heat of reaction supplied the major proportion of :the

heat required for the vaporizationof the acid and for heating it to reaction temperature, that is, over 90%.

The temperature of the exit gases was between 425 and 430 C.

v V 'ExampleIII This run was made under conditions similar to those of Example 1, except that a lower mole ratio of propane to nitric acid was used. The

propane was preheated -to about 435 C. and in troduced into the 'nitrator at 11,500 on. it-per hourand 125 lb. pressure. The nitric acid was introduced through five spray jets at the rate of.

122'lb5of 77.2% acid per hour. This corresponds to an initial mole ratio of propane to 'HNOiof '215 to -1 and an overall mole ratio 4.30 to-l.

The temperature at the center of each vapor izer-reactor sectionwas about 400 C. The tern- -perature at theexit endof each-vaporization-reaction section, where the reaction was complete and the reactant gases,.cooled during :the vaporization .of.:the acid. had ibeen -reheated.-.by h heat of reaction, held'at416-4209C.

' "During this run. :the helmet zbetweemhe c "vaporization. andlheatcfreectieh-was neatly/her.-

feete s i ht exce s of h at o ea ion. w a en car of by ntr u n a ve y am un of steam to the nitrator at those sections where the temperatures were a little higher than desired. V I 1 a J The nitroparaffins were produced at the rate lb. per hour which corresponds to a conversion of 29,9% of the nitric acid to nitroparafiins.

' Example IV Thisrunwassimilar to the preceding run, except that the nitrator consisted of four-spray vaporizer-reactor sections instead of five. The same propane rate and temperature were used. Approximately the same amount of acid was supplied to the individual spray jets, but'the overall ratio of propane to nitric acid for the entire nitrator was considerably higher. Thetotal acid rate for the four jets was 461 lb. per hour of 77.5% acid which corresponds to an overall mole ratio of propane to acid of 5.65 to '1. The ratio at the first jet was 22.6 to 1. V

Steam was added'to prevent the slightexcess of heat of reaction from causing a temperature rise. The temperature at the center of each vaporizer-reactorsection was about 400 C The exit end of each vaporization-reaction section was 415-420 C. r

The nitroparaffins were produced at the rate of 1 39 1b.,per hour which amounts to a 29.5% conversion cf nitric acid to nitroparafins.

Example V of propane rather than concurrent with it.

The nitrator consisted four spray vaporizer-reactor sections as it had in Example IV and similar acid'and propane rates were used. Propane, preheated to, about 440 C., troduced to the bottom of the nitrator at the rate of 11,500 cu. ft. per hour. The acid rate was 442 lb. per hour for the four jets. The, average acid concentration was 77.3% so that the overall mole rate of propane to acid was 5;9 tol.

.That atthe first jet was23.6 to 1.

Exit temperatures from the vaporization-reaction sections were 415-420 C. A 29.6% conversion of nitric acid to nitro parafiiris was obtained.

While the above describes the preferred embodiments of our invention, it Will be understood that departures may be made therefrom within'thescope of the specification and claim.

Thisapplication is a division of our co-pend-,

ing application, Serial No. 546,186; filed July 22,

1944, now' Patent No. 2,418,241.

'In accordance with the foregoing specification, we claim-as our invention:

An apparatus for producing an exothermic chemical reaction between a liquid reactant and a vapor reactant in which the liquid reactant is vaporizedduring the'reaction, whichcomprises chamber at the top-and also at a .pluralit got" .spacedroihts the rea tiehpehambeh hereby I was in- 9 producing a corresponding series of reaction zones at different heights in said chamber, an inlet for the vapor reactant at one end of said reaction chamber and an outlet for reaction vapors at the other end of said chamber, means for preheating the vapor reactant prior to its passage into said chamber, means for cooling reaction vapors connected to the vapor exit of said chamber, means for controlling the temperature and other conditions of the reaction mixture so that the exothermic heat of reaction in each of said reaction zones is substantially balanced by the heat required to vaporize said liquid reactant; said controlling means including auxiliary heating means mounted adjacent the liquid spraying means in each oi said reaction zones, means for cooling the reaction mixture between said auxiliary heating means and said liquid spraying ,means and thermostatic means for independently controlling the degree of cooling produced by said cooling means in each of said reaction zones; whereby optimum reaction temperatures can be maintained substantially throughout the length of said reaction chamber.

LEONARD A. STEN GEL. RICHARD S. EGLY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,086,808 Kallam July 13, 1937 2,162,158 Coey June 13, 1939 2,220,219 Crawford Nov. 5, 1940 2,300,985 Smith Nov. 3, 1942 2,330,767 Welty Sept. 28, 1943 2,374,660 Belchez et a1. May 1, 1945 2,418,857 Stratford et a1. Apr. 15, 1947 2,433,798 Voorhees Dec. 30, 1947 

